Thermic process.



UNiTE STATES PATENT ornrou HANS GOLDSCHMIDT, OF ESSEN-ON-THE-RUHR, GERMANY, ASSIGNOR TO THE FIRM OF GQLDS GHMIDT, OF ESSEN-ON-THE-RUHR, GERMANY.

'rimnmc rriocnss.

,the Goldschmidt Thermic Process, of which .the following is an exact specification.

' In another atent application Ser. No. 294971 whichil file together with-this appli cation, it has been stated that an excellent result is obtained by the employment of a mixture of calcium-silicon being used as areduc- Jng agent in metallic 'oxids, metal or halo en compounds, sulfids or in metallic sa ts. Now it has by extensive experiments been established that a mixture of calcium and aluminum, in the place of the mixture of calciumand silicon, will also 'produce a high that the use of such a metallic mixture renders possible the production of a'thinly liquid slag, to which y an addition of other substances the prop- "erty of sintering ((i. e, of coalescing or growin .into a solid mass without passing "throug astate of complete fluidity) can be given, so that it becomes possible to use this mixture for all the known applications of the 'Goldschmidt thermic process. Naturally, instead of the mixture of calcium and alu- I m1num' a calcium-aluminum alloy can be used, presenting the advantage of bein moreresistant against the atmosphere.

surprising fact when operatin with this mixture or: alloy of calcium an aluminum is,.that, while. calcium alone, brought to reaction with ,e. g.- iron oxid, produces a considerably lower caloric effect than e. g. .alu-

' minum,'although the heat of combustion of calcium is higher than, .thatof aluminum, a

much higher caloriceflect is produced when using a mixture offcalcium and aluminum.

This is clearly provided. by the following:-

'- When mixing aluminum with iron oxid, and

of iron .e ualing about one third of weight o the. mixture mayb'e added to'the liquid iron, and still the iron as well as the bringing this mixture to reaction, a

e total v slagobtained will be perfectly liquid. If.

calcium is taken, and mixed with an equivale t nantityof iron oxid andmeta'lli'c iron is adde d to theamountpf one third of the weightof the mixture, a sintering mass 15 obtained; a result, whichfis partly due to the production of a slag which fu'ses with difli- Specification of Letters Patent. .Applioation filed. iamiar s. 1996. s mi No. 294.972.

1rgiantity 1 ratented neasi, 1907.

culty. If however a mixture is taken of aluminum and calcium intimately mixed with iron oxid or iron-oxid-protoxid {Fe [Fe,] 0 in the manner of the Goldschmidt thermic process, the thermic effect considerably increased, and more thauflouble the quantity of iron, *5. e. ofthe totalmeight of the mixture can be added without causing the slag to solidify or the iron to become sluggish. This is a thermic effect which, in comparing the mixture of calcium and aluminum 'to' the pure aluminum thermit, shows the perfectsuitability of the former. In the followin a survey is given of the-knowledge gained in t e course of extensiveexperiments: It has been more and more clearly borne outby these ex periments that, for technical reasons, pure calcium alone is not suitablefor carrying out thesereactions. It has been stated-in my 0th? application, that the. reaction between cal ium and chromic oxid is only slow and results in a sintered mass. Usin other oxids e. g. vanadic oxid or the oxide of ead or' copper a more violent reaction is produced. Calcium acts most ener etically on saltpeter, and it is most remarkable that calcium mixed with ammonia} nitrate sel fi niting and burns ofl like npowder. It is urthermore known that a uminum acts very strongly on gylpsum and other sulfates suchas Glaubers sa t. Carried outwith calcium this reaction is still more energetic. .J. One fact demonstrated by the experiments was the great velocity of the reactions carried out with calcium, surpassing in rapidity the aluminum thermit mixtures. It was further shown in the course of the experiments with mixtures of calcium and alumi num withmetallicoxids, that the reaction is accelerated in. its course, and that thereby 03, is increased. It must further be mentioned that the calciumoxid with the alumi- 'num oxid forms a more thinly liquid .slag'.

It is also possible that, by theunion'of the 106 oxids of calcium and aluminum an exo-theumic effect is produced, furtheriricreasing the caloriceflec I The greatest eflicicncy and. the uietest reactions are generally-obtained wit .mix- 105 tures composed in such! we as toflgive the most 'possibly'thinly liqui slag,- a thinly liquid aluminate is calcium-aluminurn-oxid' (3CaO2Al,O,). This is actually obtainedby mixing together about60% ofauequiva- 110 the energy, created while the mixture burns a lent mixture of aluminum with iron oxid or oxydulated iron respectively (so-called ther mit) and 4:0 .of an equivalent mixture. of finely divided calcium and iron oxid; this nearly exactly corresponds withan alloy of equal parts of calcium and aluminum (to be exact 49Al5lCa).

Regarding the caloric effect of the mix tures, the calorimeter furnishes valuable indications in this respect, generally preference will be given to the mixture 'elding the highest thermic effect. Nevert eless 1t is, of course, possible, and in many instances it will be necessary, to carry out reactions with mixtures of a restricted caloric effect, be it v for the purpose of weldin or for producing metals, or for heating ot er bodies, llquids and the like. Furthermore, not only has calcium thermit (the name that may be given to a mixture consisting of about equal parts of metallic calcium and iron oxid) been admixed to the known (aluminum-) thermit,

' and the result of such mixtures been carefully observed, but mixtures consisting of the three metals calcium, aluminum and sillcon and of oxygen compounds, have also been I examined. Of course the alloy of these -manganese be added (pure or in the form of ferro-manganese).

It is clear that in practice, when choosing between all these reducible metals, not only their caloricefiiciency, but also their.at'omic weight and their equivalency will have to be considered. V

When using the mixture of the easily oxidable calcium as such, with aluminum, the contact with the air will of course, have to be avoided as much as possible and this calcium aluminum thermit will preferably be keg in air-tight receptacles.

y using an addition of calcium for the reactions a better separation of the metal. is' frequently achieved in. cases where with aluminum alone uniform reguli could not be obtained.

Hereinafter various of the so-called thermlt-mixtures are enumerated 'and the results described.

An addition of silicon to the aluminum produces, as already known, the. effect. of considerably lowering the caloric effect-of the thermit mixtures, so that e. g. with an addition of 17% of silicon to the aluminum,

the amount of "heat yielded by such a mixture, if compared to the mixture made 'oxid on the other.

and 100 parts silicon t ermit. loric efiect is lower than that of the known 'different proportions. (19., c

with aluminum (the ordinary trade thermit) is only about 75%. In consequence of the lively reactions which result when calcium alone is mixed with oxids or chlorids, it is not easy to make these determinations in the ordinary calorimeter; as a matter of fact these determinations, if carried out under equal conditions, give a.

much lower figure for thermit made with calcium alone than for the ordinary trade thermit. Mixtures of calcium and iron oxid will still yield small quantities of metallic iron, but owing to the limited fluidity of the slag, the separation is insufficient for practical purposes, and a characteristic sign of the actually lower caloric, i. e., practical efliciency is to be seen in the fact that, as

soon as even small quantities only of metallic iron are added to the calcium-thermit, the

mass only still sinters, whereas to the ordinary thermit and to the so -called' 'calcium-aluminum-thermit large quantities Of iron may be added without causing the mass to sinter. On the other hand, the amount of heat produced is considerably larger in the case of calcium-siliciumbeing used than with calcium alone (subject matter of my second application) especially when operating with mixtures or alloys containing as reducing agent two parts calcium and 1 part silicon. But these mixtures do not- "either come up to the ordinary thermit. The best result is achieved by alumimimto. which anequal part of calcium is added. The mixture may consist of 40% of an about equivalent mixture of calcium and iron oxid on the one side, and of 60% of an equivalent mixture of aluminum and iron The same proportion is to be observed when reducing chromium oxid to chromium, if a good result is to be obtained. Another mixture givi similarly good reuslts is: 70 kg calcium l'iermit'and 30 kg aluminum thermit.

As regards calcium aluminum siliciumiio thermit a good result and a highly thinly-g liqluid slag are yielded by a mixture of metals w ich after the reaction leaves a slag of the following composition: Calcium-aluminumsilicon-oxid (3OaO.Al,O Si.3O,) and which accordingly would have to consist of 50 parts aluminum-thermit, 7 0 arts calcium thermit aluminum-thermit (about 75%)v but the mixture is. still suitable'for technical purposes-especially for welding. The thermic effect is not greatly diminished by using aluminum, silicon and calcium in slightly equal portions of aluminum-siliciuman alcium-thermit,

Still the caor two portions of aluminum, 1 portion of silicon and 1 portion ofcalcium-thermit or 1 portion of aluminum, 1 portion of siliconand two portions of calcium-thermit. The last 13o mentioned mixture is the least efiicient one more readil as far as heat production is concerned.

With reference to the reduction of other -metals, it may be mentioned that e. g.

GhI'OhliG oxid. is very efiectivelyreduced by a mixture of calcium and aluminum, the best reduction is when yielding a slag according to formula calc um-aluminum-oxid (3'CaO2A1 OQ. A good reguline extraction of manganese is effected by calcium and silicon, whereas chlorid of manganese is produced b calciumand silicon than by ca 0mm and a uminum. Sulfid of copper again is very easily reduced into a regulus' by calcium-aluminum than by'calcium-silicon. Sulfid of lead mixed with calcium alone, "explodes with a strong detonation on being ignited, whereas the reaction is very quiet ,when' using calcium and silicon, and, a good reguline separation takes place when using calcium and alumi- I quarter to t num.

Having thus fully described the nature of my invention, what I desire to secure by Letters Patent of the United States is 1. A thermic mixture, consisting of metallic substances, containing calcium, aluminum and a metalliccom ound ca able ofbeing reduced to a .metai: the su stances'being thoroughly mixed with each other and the proportions of the two active reducing metals bein such that calcium forms one quarter to Ehree' quarters in weight of the weight of the two active metals.

2. A thermic mixture consisting of metallic substances, containing calcium and aluminum in form of an alloy and ametal compound capable of being reduced to a metal, the substances being thorou hly mixed with each other, and the r0 ort ons of the two active reducing metalls eing such that calcium,forms one quarter to three quarters in weight of theweight of the two active metals.

3. A thermic mixture consisting of metalalumi lic substances, containing calcium and num and a metal compound containing only metal. and oxygen, the substances belng thoroughly mixed with each other and the proportions of the two act ve reducing metals bein such, that calciumiorms one ree quarters in weight of theweight of the two. active metals;

4. A thermic mixture cons st ng of metallic substances containing calcium and aluminum in form of an alloy and a metal com- &

pound containing only metal and oxygen,

the substances beingthOroughJy mixed. with each other and the pro ortions of the two active reducing metals eing such that cal cium forms one quarter to three quarters in Weight of the weight of the two active metals.

5. A thermic mixture consisting ofmetallic substances containing calcium and alumi, num and an iron-oxid compound the substances being thoroughly mixed with each ot er.

* 6,. A thermic mixture consisting of metal-- lic substances containin calcium and aluminum and of "iron-oxid e 0 and iron-oxidprotoxid (Fe O,,), the substances'being thoroughly mixed with each other. i

7. A thermic mixture consisting of metallic substances containing calcium and aluminum in form of an alloy and of an i ron-oxid compound the substances being thoroughly mixed with each other.

8'. A thermic mixture consisting of metal- ,lic substances containing calcium and aluminum in form of an alloy and of iron-oxid (Fe O' and of iron-oxid-protoxid(Fe O,) the substances being thoroughly xed Wlth each other. a. a

9. A thermic mixture consisting of metallic substances containing calcium and alumi-- num and (of other active metals 'and of an iron oxid compound the substances being thorou hly mixed with each other.

10. thermic mixture consisting of metallic substances containing about 40 per cent. of a mixture of calcium with an, iron-oxid compound and about 60 per cent. of a mixture of aluminum with an iron-oxid compound. i i

11. Athermic mixture consisting of metallic substances containing about 40 er-"cent. of a mixture of calcium with ron-oxid (Fe O and iron-oxid protoxid (Fe Og and about 60 per cent. of a mixture of aluminum with iron-oxid (Fe O and toxid (Fe O .In witness iron-oxid-prohereof I have hereunto set my hand in the presence of two witnesses.

HANS GOLDSCHMIDT. Witnesses: v I 'WOLDEMAR HAUPT, HENRY HASRER. 

